EP1383137B1 - Verfahren zum immobilisieren Natriummetall in Glas - Google Patents

Verfahren zum immobilisieren Natriummetall in Glas Download PDF

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Publication number
EP1383137B1
EP1383137B1 EP03291449A EP03291449A EP1383137B1 EP 1383137 B1 EP1383137 B1 EP 1383137B1 EP 03291449 A EP03291449 A EP 03291449A EP 03291449 A EP03291449 A EP 03291449A EP 1383137 B1 EP1383137 B1 EP 1383137B1
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EP
European Patent Office
Prior art keywords
sodium
reactor
vitrified matrix
oxide
vitrified
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EP03291449A
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English (en)
French (fr)
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EP1383137A1 (de
Inventor
Philippe Mulcey
Jean-Yves Frayer
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Technip Energies France SAS
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Technip France SAS
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Classifications

    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/04—Treating liquids
    • G21F9/06—Processing
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/005—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture of glass-forming waste materials
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/002—Use of waste materials, e.g. slags
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/0042—Compositions for glass with special properties for glass comprising or including particular isotopes
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/28—Treating solids
    • G21F9/30—Processing
    • G21F9/301—Processing by fixation in stable solid media
    • G21F9/302—Processing by fixation in stable solid media in an inorganic matrix
    • G21F9/305—Glass or glass like matrix
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S423/00—Chemistry of inorganic compounds
    • Y10S423/09—Reaction techniques
    • Y10S423/12—Molten media

Definitions

  • the present invention relates to a process for the immobilization of metallic sodium in the form of glass, which can be used in particular to carry out the vitrification of metallic sodium containing radioactive elements, such as sodium used in the liquid state in certain nuclear installations. , as for example in the primary or secondary circuits of nuclear reactors of the fast neutron die.
  • the liquid sodium resulting from an implementation in a nuclear installation may have variable contents of radioactive elements, such as 22 Na, tritium or 137 Cs.
  • radioactive elements such as 22 Na, tritium or 137 Cs.
  • the sodium present in certain pilot reactor test loops may contain more than 0.001% by mass of radioactive elements
  • the sodium resulting from an implementation in a primary or secondary circuit of a conventional nuclear reactor of the fast neutron channel is generally a weakly radioactive sodium, which usually contains about 10 -12 g of radioactive elements per gram, these radioactive elements also having a short half-life and descendants stable.
  • the sodium resulting from implementation in a nuclear installation is considered, in view of the current legislation, as a nuclear waste as such, potentially contaminating for the external environment.
  • this sodium is at least classified as nuclear waste known as "very low activity” (TFA). Therefore, during deconstruction operations of nuclear facilities using sodium, it is necessary to store this sodium, so as to avoid contact with the external environment, regardless of its degree of contamination.
  • glass-like matrices are generally the most interesting.
  • the term "glass” in the sense of the present description must be understood in its broadest sense in the field of vitrification of waste, that is to say, a relatively homogeneous solid mixture of different mineral constituents, generally at silica base, being in the form of a non-porous solid, advantageously formed of chemically and structurally bonded elements, and suitable for immobilization of waste.
  • the term "glass” in the sense of the invention preferably denotes a solid specifically having an amorphous structure. In some cases, this term may nevertheless also designate solids having a partially crystalline structure, especially of the crystalline type, or even crystalline solids.
  • the term “glass matrix” refers to any solid matrix having a continuous phase based on a "glass” in the sense of the invention.
  • the glass-type matrices have a much lower specific surface area than the cement-type matrices, particularly insofar as they are not porous. They therefore offer a greatly reduced exchange surface with the external environment.
  • composition of this sodium-based matrix is desirable for the composition of this sodium-based matrix to be as homogeneous as possible.
  • vitrified matrices really interesting, it is therefore necessary to achieve the immobilization of sodium in these matrices under the most controlled conditions possible.
  • This process makes it possible to obtain vitrified matrices of homogeneous composition and which may have low lixiviation levels as a function of the amounts of silica, alumina, quicklime and boron oxide introduced.
  • this process involves the use of large quantities of air, only part of which is consumed by the sodium oxidation reaction, which has the disadvantage of leading to the production of gaseous effluents in large quantities. reactor outlets, which are likely to carry radioactive dust, which, again, translates into the cost of effluent treatment and potential environmental impact.
  • vitrification process without significant production of gaseous effluents allowing, within a single reactor, to prepare, from sodium metal, a vitrified matrix of homogeneous composition integrating sodium in the form of an oxide.
  • the present invention aims to provide a sodium immobilization process within a vitrified matrix, adapted to achieve sodium containment comprising radioactive elements.
  • one of the aims of the invention is in particular to provide a method of immobilizing sodium limiting the possible exchanges between the contaminated sodium and the external medium.
  • the object of the invention is also to provide a process for the immobilization of metallic sodium in the form of a glass, which is both simple to implement and where the final composition of the vitrified matrix obtained can be modulated easily according to the properties sought for this matrix, especially in terms of resistance to leaching and devitrification.
  • the mineral matrix precursor (i) of the invention may consist of any mixture of particles based on oxides, carbonates or salts commonly used in the constitution of glasses.
  • it may in particular be chosen from mixtures generally referred to as "raw material” used in the constitution of so-called “nuclear” glasses used to carry out the confinement of radioactive waste.
  • the vitrified matrix precursor (i) may for example consist at least in part of solid particles comprising particles based on silicon oxide SiO 2 , generally in combination with particles based on CaO calcium oxide and and / or boron oxide B 2 O 3 , optionally in combination with particles based on aluminum oxide and / or magnesium oxide, the particles based on the various oxides mentioned above being able to be particles based on only one of these oxides, or based on a combination of two or more of these oxides.
  • the vitrified matrix precursor (i) is specifically introduced into the reactor where the process of the invention is carried out in dispersed form.
  • it is generally introduced in the form of a mixture of particles, generally particles of metal oxides, or particles of preformed glass frits, these particles preferably having an average size of between 0.1 and 20 millimeters, advantageously less than 10 millimeters, and preferably less than 5 millimeters.
  • the vitrified matrix precursor of the invention can advantageously be used in the form of a mixture of particles of silica, alumina, quicklime and boron oxide with particle sizes of between 1 and 3 millimeters. .
  • these frits of glasses can also be used in the form of glass frits, in particular in the form of glass frits based on oxides of silicon, aluminum, calcium and boron, these frits of glasses advantageously having an average size of between 1 and 10 millimeters, and preferably less than 5 millimeters.
  • the metallic sodium used in the process of the invention may advantageously be a sodium containing radioactive elements, and it may in particular be sodium from a primary or secondary circuit of the nuclear reactor of the sector. called fast neutrons.
  • the sodium can be introduced into the reactor in the form of liquid droplets, preferably between 10 microns and 500 microns, preferably less than 200 microns and preferably between 50 and 150 microns, these droplets being most often obtained by spraying the liquid sodium, for example by means of an injection nozzle.
  • the sodium introduced may also be derived from a premix of dispersed liquid sodium with at least a portion of the vitrified matrix precursor.
  • the dispersed sodium that is introduced is in the form of sodium deposited on vitrified matrix precursor particles.
  • the sodium in the dispersed state which is introduced in step (A) of the process may for example be in the form of silica particles on the surface of which sodium is deposited.
  • the incorporated sodium content is less than 30% by weight, and advantageously less than 20% by weight, relative to the total mass of the matrix. It is furthermore preferred that this level of incorporated sodium be greater than 4% by weight, and advantageously 5% by weight, relative to the total mass of the matrix. Thus, this level is typically between 5% and 15% by weight relative to the total mass of the matrix.
  • the mass of sodium metal introduced into the reactor is between 3% and 20% by weight relative to the mass of vitrified matrix precursor introduced.
  • this mass of sodium introduced is less than or equal to 14% by weight, and preferably less than or equal to 12% by weight, relative to the mass of vitrified matrix precursor introduced.
  • the vitrified matrix precursor is based on silicon oxide, which is generally the case, it is preferred that the molar ratio of the amount of sodium introduced relative to the amount of silicon introduced into the breast.
  • the vitrified matrix precursor is between 1: 20 and 1: 1, and advantageously less than 1: 6.
  • iron oxide Fe 2 O 3 This constituent ensures in the reactor the conversion of sodium into oxide, the form in which sodium is effectively integrated within the vitrified matrix, specifically as a constituent element of this matrix, and not as an inclusion element.
  • Iron is also a structural forming element, in the same way as silicon or aluminum. In particular in the presence of these silicon and aluminum elements, the iron forms by interconnections, the vitreous network. It is also likely to lead to the formation of mineral structures known to include cavities capable of trapping certain radioactive contaminants possibly present in sodium.
  • the iron oxide Fe 2 O 3 be introduced into the reactor in a dispersed form, in particular so as to ensure a maximum of contact interfaces between this oxide and sodium, also introduced under a dispersed form with a high exchange surface. Therefore, it is generally preferred that the iron oxide Fe 2 O 3 be introduced in the form of particles comprising Fe 2 O 3 iron oxide, these particles preferably consisting essentially of Fe 2 iron oxide. O 3 , and advantageously having a mean size of between 0.1 and 20 millimeters, particularly preferably less than 10 millimeters, and advantageously less than 5 millimeters. It is preferred that the specific surface area of these particles be as high as possible.
  • the amount of Fe 2 O 3 iron oxide introduced is also decisive for ensuring effective oxidation of the sodium introduced into the metallic state. Indeed, it is necessary that Fe 2 O 3 iron oxide is introduced in sufficient quantity to ensure this oxidation.
  • the molar ratio of the amount of iron introduced in the form of iron oxide Fe 2 O 3, based on the quantity of sodium introduced is between 0.5: 1 and 3: 1. To preferably, this molar ratio is greater than or equal to 0.6: 1, and advantageously greater than or equal to 0.9: 1. Moreover, it is generally preferred that this molar ratio is less than 2: 1, and advantageously less than 1.5: 1.
  • the vitreous matrix obtained in fine generally contains iron oxides FeO and / or Fe 3 O 4 , or residual Fe 2 O 3 oxides.
  • the mass of Fe 2 O 3 introduced is between 5% and 50% by weight based on the matrix precursor introduced vitreous mass, and preferably in an amount of less than 35% by weight, preferably less than 30% by weight, and more preferably less than 25% by weight.
  • the constituents (i), (ii) and (iii) of step (A) of the process of the invention are generally introduced in the absence of any trace of water. , so as to avoid any reaction of sodium with water, which would be likely to lead both to the production of a hydrogenated gaseous effluent, and to embrittlement of the vitrified matrix obtained in fine.
  • the vitrified matrix precursor and the Fe 2 O 3 iron oxide used are generally dried and then stored protected from any trace of moisture.
  • the solids introduced into the reactor can be transported by small amounts of carrier gas.
  • the carrier gas is generally free of any trace of water, and is preferably an inert gas such as nitrogen. This carrier gas is only likely to lead to the formation of low flow rates of gaseous effluents, which is particularly advantageous when the process is conducted on sodium containing radioactive elements (limitation of secondary effluents).
  • step (A) of the process of the invention are generally introduced into the reactor at a temperature ranging from 15 ° C. to 150 ° C.
  • sodium is generally introduced in the liquid state, that is to say at a temperature preferably greater than 100 ° C, most often between 110 ° C and 130 ° C, and the other components can be introduced at lower temperatures for example between 15 ° C and 100 ° C, typically between 20 and 60 ° C.
  • the homogeneous mixture of step (B) of the process carried out by contacting the various constituents (i), (ii) and (iii) in dispersed form, is generally carried out by introducing the vitrified matrix precursor and the oxide of iron within the reactor in the form of a rain of particles and spraying the sodium in the liquid state within said rain of particles.
  • particle rain in the sense of the invention is meant a falling dispersion of particles, advantageously dispersed so homogeneous, of the type used in reactors using reagents in pulverulent or dispersed form.
  • Rainfall particles according to the invention can be made using any type of conventional powder dispersion system known from the state of the art.
  • the precipitation of particles based on the vitrified matrix precursor and the iron oxide is advantageously carried out from an initial mixture of the iron oxide (iii) with the vitrified matrix precursor (i), but it can alternatively be obtained by interpenetration of two or more rays of iron oxide and vitrified matrix precursor particles.
  • Another embodiment of the mixture of step (B) comprises depositing the sodium on at least a portion of the vitrified matrix precursor particles, generally on silica particles, and then mixing the constituents (i), (ii) and (iii) by interpenetration of two particle rains comprising, for one of the Fe 2 O 3 -based particles, and for the other, the vitrified matrix precursor particles of which at least a part is impregnated by sodium.
  • step (B) it is generally preferred, particularly so as to optimize the sodium oxidation reaction in situ, that the homogeneous mixture produced during step (B) is brought to a temperature of between 150 ° C and 400 ° C prior to the heat treatment of step (C).
  • components (i), (ii) and (iii) are homogeneously mixed at a temperature below 150 ° C, and then brought to the temperature conditions of step (C), c. ie at a temperature of 1000-1600 ° C, and preferably between 1400 and 1500 ° C, according to a rising temperature gradient.
  • the reactor used in the process of the invention preferably comprises an upper part at a temperature of between 100 ° C. and 150 ° C., where the mixing step (B) and a low part take place.
  • step (C) under the temperature conditions of step (C), that is to say at a temperature of 1000-1600 ° C, and preferably at a temperature between 1400 and 1500 ° C, the constituents of step (A) ) being introduced into the upper part of the reactor where their mixing takes place.
  • the preferred configuration of the reactor proposed above allows a flow of the glass crust formed towards the lower zone of the reactor under the temperature conditions of step (C), ie at a temperature of temperature of 1000-1600 ° C, where it is melted within the reaction mixture, which avoids a blockage of components (i), (ii) and (iii) at the top of the reactor, which would have the effect of reducing the effectiveness mixing these constituents and / or limiting the yield of the sodium oxidation reaction.
  • the heat treatment step (C) may be carried out according to any means known to those skilled in the art, suitable for producing a vitrified matrix.
  • the residence time of the mixture under the temperature conditions of step (C) must naturally be sufficient to bring the homogeneous mixture from step (B) under said temperature conditions.
  • Step (C) of the process of the invention may for example be carried out by heating the walls of the reactor in which the process of the invention is carried out, in particular by the Joule effect.
  • step (C) of the process of the invention is carried out by means of induction heating.
  • induction heating in the context of the production of a glass is a known and widely described technique, which is based on the fact that glass, insulating at low temperature, becomes conductive under the effect of a temperature increase.
  • the use of induction heating is particularly advantageous, insofar as it can make it possible to form on the walls of the reactor a cooled glass layer which acts as a protective layer for the reactor throughout the process. which is particularly interesting in the case where it is desired to carry out the process by ensuring optimal confinement conditions.
  • Such a technique generally referred to as induction heating "in a self-cooled crucible"
  • induction heating in a self-cooled crucible
  • step (C) it is possible, during step (C), to convert at least a portion of the iron oxides FeO and / or Fe 3 O 4 resulting from the oxidation reaction.
  • sodium in the form of oxide Fe 2 O 3 which participates more effectively in the constitution of the glass matrix than FeO or Fe 3 O 4 oxides.
  • oxygen is injected in a controlled manner into the mixture of step (C).
  • the amount of oxygen used in this context is preferably to be adapted so that all the oxygen introduced is consumed, so that the oxygen introduced is not likely to lead to the formation of gaseous effluents, nor to lead to obtaining bubbles within the final vitreous matrix. It is often preferred to use particles (iii) of Fe 2 O 3 iron oxides having the highest possible specific surface area.
  • steps (A) to (C) of the process of the invention are decisive for obtaining a homogeneous composition within the vitrified matrix obtained according to the process of the invention
  • the formation step (D) of the vitrified matrix from the melt mixture from step (C) as for it is an important step especially with regard to the physical properties of the vitrified matrix obtained.
  • the vitrified matrix obtained has as little exchange surface as possible with the external environment.
  • the vitrified material obtained has a high resistance to rupture.
  • Step (D) generally consists in a casting operation of the melt mixture (magma) from step (C) in an ingot mold or in metal containers, usually steel drums. .
  • the magma obtained by casting can be rolled.
  • the cooling of the composition is generally carried out under conditions such that they limit the risk of occurrence of micro-fractures by thermal shock.
  • Another way of limiting the risks of occurrence of micro-fractures by thermal shock is to use boron oxide B 2 O 3 as constituent of the mineral matrix precursor (i).
  • the process of the invention can be carried out in a continuous mode, that is to say by continuous addition of constituents (i), (ii) and (iii) within the reactor, and casting continuous mixing from step (C) at the outlet of the reactor.
  • a continuous mode that is to say by continuous addition of constituents (i), (ii) and (iii) within the reactor, and casting continuous mixing from step (C) at the outlet of the reactor.
  • a bath of molten glass In the context of a continuously conducted process, it is generally necessary to form in the reactor a bath of molten glass, most often at a temperature of between 1000 ° and 1600 ° C., preferably at a temperature of temperature above 1200 ° C, and advantageously greater than 1400 ° C, typically between 1400 and 1500 ° C.
  • This bath is generally obtained according to a preliminary step of introducing only vitrified matrix precursors into the reactor to undergo a heat treatment step at 1400-1500 ° C, which is generally conducted under the conditions of the step ( C) defined above.
  • obtaining this glass bath is obtained by induction, preferably under the conditions of production of a "cooled self-crucible" as defined above.
  • the ratio of the mass flow rate of sodium metal introduced, relative to the mass flow rate of vitrified matrix precursor introduced is between 0.03 and 0.3, advantageously, this mass ratio is less than 0.2, and preferably less than 0.14. Typically, it is between 0.05 and 0.12.
  • the ratio of the molar flow rate of iron introduced in the form of iron oxide Fe 2 O 3 , based on the molar flow rate of sodium introduced is in turn preferably between 0.5: 1 and 3: 1, and it is advantageously greater or equal to 0.6: 1, and preferably greater than or equal to 0.9: 1.
  • this ratio of Fe / Na molar flow rates be less than 2: 1, and advantageously less than 1.5.
  • the ratio of the mass flow rate of Fe 2 O 3 introduced, based on the mass flow rate of introduced vitrified matrix precursor is generally between 0.05 and 0.5. This ratio is preferably less than 0.35, and preferably less than 0.3.
  • the inlet flow rates of the constituents (i), (ii) and (iii) as well as the flow rate of the melt mixture at the reactor outlet can vary in a rather large measure depending on the amount of sodium that it is desired to treat.
  • the process of the invention makes it possible to achieve flow rates of the relatively high melt glass composition typically between 0.4 and 1.5 tons per hour.
  • the inflow different constituents are generally 15 to 160 kg per hour for sodium, 60 to 540 kg per hour for iron oxide Fe 2 O 3 , and 325 to 800 kg per hour for the vitrified matrix precursor
  • This reactor vacuum is part of the so-called “dynamic containment” measures, advantageously implemented in the context of the treatment of radioactive waste, which aim to prevent any release of waste to the outside environment (in case of accidental leakage, there is a transfer of the external environment to the contaminated medium and not the opposite).
  • Such a hold under vacuum certainly implies very small gaseous effluents but the control of these minor effluents can be ensured simply and effectively by usual means, commonly used in the field of the treatment of radioactive gaseous effluents, such as filters of the category called “very high efficiency", or activated carbon filters.
  • the metallic sodium (ii) can be introduced during step (A) together with another alkali metal in metallic form, generally metallic potassium.
  • sodium (ii) is generally part of a Na / K mixture, most often in liquid form.
  • This Na / K mixture can in particular be a mixture of the type of those used in the cooling circuits of nuclear installations, and it can therefore be understand radioactive elements.
  • the process of the invention advantageously carried out in a continuous mode, makes it possible to immobilize all the alkali metals present, as well as the radioactive elements that they possibly comprise, in the form of a glass.
  • the different conditions set out above with respect to the different mass and molar ratios to be respected preferentially to lead the process under optimum vitrification conditions are nevertheless to be adapted, by transposing the indications given. for sodium alone to all the alkali metals present.
  • the total alkali metal content incorporated in the final matrix will advantageously be less than 30% by mass
  • the total mass of the introduced alkali metals, including sodium ( ii) will preferably be between 3 and 25% by weight relative to the mass of precursor (i).
  • the amount of iron oxide (iii) used is generally such that the molar ratio of the amount of iron introduced, relative to the amount of alkali metals in metallic form, comprising the sodium metal (ii), is between 0.5: 1 and 3: 1.
  • a vitrification reactor implementing the method of the invention can be directly installed on a site being deconstruction, where it can be used to treat sodium, usually directly from the cooling circuits, without having to carry out a prior transport of this sodium, which further minimizes the risk of contamination of the external environment.
  • the process can be implemented under extremely high confinement conditions, compatible with the current legislation for the treatment of nuclear waste.
  • the method of the invention makes it possible, subject to suitably adapting the nature and the proportions of the various constituents (i), (ii) and (iii), to obtain vitrified matrices which have a homogeneous composition, are stable over time and mechanically resistant, with little or no prone to sodium leaching and devitrification, making them prime matrices for sodium containment including radioactive elements in the form of glass packages .

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Claims (21)

  1. Verfahren zur Immobilisierung von metallischem Natrium in Form von Glas, umfassend die Schritte, bestehend aus:
    (A) Einbringen ins Innere eines Reaktors:
    (i) einen Vorläufer einer glasierten Matrix:
    (ii) Natrium in metallischem Zustand;
    und
    (iii) Eisenoxid, Fe2O3, in einer Menge, die ausreichend ist, um die Oxidation des eingebrachten metallischen Natriums (ii) sicherzustellen,
    wobei diese Bestandteile (i), (ii) und (iii) spezifisch in einer dispergierten Form in den Reaktor eingebracht werden:
    (B) Erzeugen eines homogenen Gemisches dieser Bestandteile durch Inkontaktbringen der Bestandteile (i), (ii) und (iii) in dispergierter Form im Inneren des Reaktors;
    (C) Erhitzen des erhaltenen Gemisches auf eine Temperatur, die zwischen 1000 und 1600°C beträgt, wodurch man ein homogenes Gemisch im geschmolzenen Zustand bildet, in welchem sich das ursprünglich eingebrachte Natrium im Zustand von Natriumoxid befindet; und
    (D) Zurückerlangen des auf diese Art erhaltenen geschmolzenen Gemisches, und Unterziehen desselben einer Abkühlung, wodurch man eine glasierte Matrix erhält aus einer homogenen Zusammensetzung, worin das ursprünglich eingebrachte Natrium als diese glasierte Matrix bildendes Oxid enthalten ist.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das verwendete metallische Natrium radioaktive Elemente enthält.
  3. Verfahren nach Anspruch 1 oder nach Anspruch 2, dadurch gekennzeichnet, dass der Vorläufer der glasierten Matrix (i) feste Teilchen enthält basierend auf:
    - Siliziumoxid SiO2; und
    - Kalziumoxid CaO und/oder Boroxid B2O3.
  4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, dass die im Vorläufer der glasierten Matrix vorliegenden Teilchen eine Durchschnittsgröße zwischen 0.1 und 20 Millimetern aufweisen.
  5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass das verwendete metallische Natrium in Form von flüssigen Tröpfchen in das Innere des Reaktors eingebracht wird.
  6. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass das verwendete metallische Natrium in der Form eingebracht wird, dass das Natrium auf mindestens einem Teil der Teilchen des Vorläufers der glasierten Matrix abgelagert wird.
  7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass die Masse des eingebrachten metallischen Natriums zwischen 3 % und 20 % an Masse im Vergleich zu der Masse des eingebrachten Vorläufers der glasierten Matrix (i) beträgt.
  8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass das Eisenoxid Fe2O3 in Form von Teilchen eingebracht wird, die Eisenoxid Fe2O3 umfassen, und eine Durchschnittsgröße zwischen 0,1 und 20 Millimetern aufweisen.
  9. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass das molare Verhältnis der Menge an in Form von Eisenoxid Fe2O3 eingebrachtem Eisen bezogen auf die Menge an eingebrachtem Natrium zwischen 0,5:1 und 3:1 beträgt.
  10. Verfahren nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass die Masse an eingebrachtem Fe2O3 zwischen 5% und 50 % an Masse im Vergleich zur Masse an eingebrachtem Vorläufer der glasierten Matrix beträgt.
  11. Verfahren nach einem der Ansprüche 1 bis 10. dadurch gekennzeichnet, dass das homogene Gemisch aus Schritt (B) dadurch erzeugt wird, dass der Vorläufer der glasierten Matrix und das Eisenoxid im Inneren des Reaktors in Form eines Teilchenregens eingebracht werden, und das Natrium in flüssigem Zustand ins Innere dieses Teilchenregens gesprüht wird.
  12. Verfahren nach einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, dass das in Schritt (B) erzeugte homogene Gemisch vor der thermischen Behandlung in Schritt (C) auf eine Temperatur, die zwischen 150°C und 400°C beträgt, gebracht wird.
  13. Verfahren nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, dass Schritt (C) durch Erhitzen über Induktion realisiert wird.
  14. Verfahren nach einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, dass das Verfahren ein Verfahren ist, das nach einem kontinuierlichen Modus durchgeführt wird.
  15. Verfahren nach Anspruch 14, dadurch gekennzeichnet, dass das Verhältnis des Massendurchsatzes an eingebrachtem metallischem Natrium bezogen auf den Massendurchsatz an eingebrachtem Vorläufer der glasierten Matrix zwischen 0,03 und 0,3 beträgt.
  16. Verfahren nach einem der Ansprüche 14 oder nach Anspruch 15, dadurch gekennzeichnet, dass das Verhältnis des molaren Durchsatzes an Eisen, eingebracht in Form von Eisenoxid, Fe2O3, bezogen auf den Durchsatz an eingebrachtem Natrium zwischen 0,5:1 und 3:1 beträgt.
  17. Verfahren nach einem der Ansprüche 14 bis 16, dadurch gekennzeichnet, dass das Verhältnis des Massendurchsatzes an eingebrachtem Fe2O3 bezogen auf den Massendurchsatz an eingebrachtem Vorläufer der glasierten Matrix zwischen 0,05 und 0,5 beträgt.
  18. Verfahren nach einem der Ansprüche 1 bis 17, dadurch gekennzeichnet, dass das Verfahren in einem Reaktor durchgeführt wird, der bei Unterdruck gehalten wird.
  19. Verwendung des Verfahrens nach einem der Ansprüche 1 bis 18 zum Erzeugen der Beschränkung von radioaktiven Elementen, die in metallischem Natrium vorliegen, in einer glasierten Matrix.
  20. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass in Schritt (A) das metallische Natrium (ii) gemeinsam mit einem anderen Alkalimetall in metallischer Form eingebracht wird, insbesondere in Form eines Na/K-Gemisches, welches radioaktive Elemente enthalten kann.
  21. Verwendung des Verfahrens nach Anspruch 20 zum Erzeugen der Beschränkung von radioaktiven Elementen, die in einem Gemisch aus Alkalimetallen vorliegen, welches metallische Natrium enthält, in einer glasierten Matrix.
EP03291449A 2002-06-19 2003-06-16 Verfahren zum immobilisieren Natriummetall in Glas Expired - Lifetime EP1383137B1 (de)

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FR0207582A FR2841370B1 (fr) 2002-06-19 2002-06-19 Procede d'immobilisation de sodium metallique sous forme de verre
FR0207582 2002-06-19

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US7550645B2 (en) * 2004-02-23 2009-06-23 Geomatrix Solutions, Inc. Process and composition for the immobilization of radioactive and hazardous wastes in borosilicate glass
FR2888576B1 (fr) * 2005-07-15 2007-09-28 Commissariat Energie Atomique Procede de confinement d'une matiere par vitrification
EP2004561A4 (de) * 2006-03-20 2011-11-09 Geomatrix Solutions Inc Verfahren und zusammensetzung zur immobilisierung von hochalkalischen radioaktiven und gefährlichen abfallstoffen in silikatbasiertem glas
JP5159971B1 (ja) * 2011-09-15 2013-03-13 太平洋セメント株式会社 放射性セシウムの除去方法、及び、焼成物の製造方法
WO2014068643A1 (ja) * 2012-10-29 2014-05-08 太平洋セメント株式会社 放射性セシウムの除去方法、及び、焼成物の製造方法
FR3037058B1 (fr) * 2015-06-05 2017-06-23 Areva Nc Outil de lissage en milieu radioactif, comprenant une grille vibrante

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US3265627A (en) * 1965-03-04 1966-08-09 Walter E Clark Addition of lithium values in conversion of fission-product wastes to a glass-like solid for disposal
JPS5450800A (en) * 1977-09-30 1979-04-20 Toshiba Corp Removing device of radioactive substance
US4234449A (en) * 1979-05-30 1980-11-18 The United States Of America As Represented By The United States Department Of Energy Method of handling radioactive alkali metal waste
JPS60114799A (ja) * 1983-11-28 1985-06-21 動力炉・核燃料開発事業団 放射性ナトリウムの処理方法
DE3721641C1 (de) * 1987-07-01 1989-01-12 Thyssen Stahl Ag Verfahren zur Herstellung von Warmband
US4898692A (en) * 1988-11-16 1990-02-06 The United States Of America As Represented By The United States Department Of Energy Process for direct conversion of reactive metals to glass
US5461185A (en) * 1994-04-19 1995-10-24 Forsberg; Charles W. Radioactive waste material disposal
BE1010854A3 (fr) * 1997-01-15 1999-02-02 En Nucleaire Etablissement D U Procede d'oxydation d'au moins un metal alcalin.
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JP4393800B2 (ja) 2010-01-06
US7090827B2 (en) 2006-08-15
FR2841370B1 (fr) 2004-08-06
RU2318259C2 (ru) 2008-02-27
FR2841370A1 (fr) 2003-12-26
ATE405934T1 (de) 2008-09-15
DE60323016D1 (de) 2008-10-02
JP2004037458A (ja) 2004-02-05
US20040024277A1 (en) 2004-02-05

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